c cxnh



DERIVATIVES O1 4:4-BIAMINOSTILBENE DISULFQNIC AQID-(Zfl') Adolf Emil Siegrist, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application September 11,1952, Serial No. 309,135

Claims priority, application Switzerland September 13, 1951 8 Claims. (Cl. 260249.6)

The present invention relates to derivatives of 4:4-diaminostilbene disulfonic acid-(2:2) of the general formula in which v, w and 2 indicate NHz or the residue of a primary or secondary amine which is attached by the nitrogen atom to the triazine ring, and x and y indicate chlorine, the residue of an aromatic hydroxyl compound attached by way of an O bridge to the C-atom of the triazine ring, or of an aliphatic or aromatic mercapto compound attached by an S bridge to the C-atom of the triazine ring, or a residue of the kind of w or z, and the salts thereof.

The compounds of the general formula set forth, or the salts thereof, are obtained when, in suitable sequence, according to conventional methods, 2 mols of a 4-aminostilbene disulfonic acid-(2:2') which contains in the 4'- position a group convertible into an amino group, or a salt thereof, are reacted with 3 mols of cyanuric chloride and 3-5 mols of ammonia or 3-5 mols of an amino compound containing a primary or secondary amino group, or with 2 mols of an aromatic hydroxyl compound and 3 mols of ammonia or 3 mols of an amino compound containing a primary or secondary amino group or with 2 mols of an aliphatic or aromatic mercapto compound and 3 mols of ammonia or 3 mols of an amino compound containing a primary or secondary amino group, the group which is convertible into an amino group being converted into such a group at a suitable stage of the intermediate products produced.

Thenew compounds of the formula set forth and also the salts thereof have no dyestuif character in the narrow sense but, according to their constitution, possess a more or less pronounced'aflinity for various substrata, such as vegetable fibers. On these substrata they exhibit a blue to violet fluorescence in ultraviolet light. On account of this property, the products of the invention are capable of improving the white content in the case of undyed material and the purity of the shade in the case of dyed material.

As 4-aminostilbene disulfonic acids-(2:2') which con tain in 4-position a group convertible into an amino group,

" there are concerned, for example, such as contain an acylamino group in 4-position. Preferably however 4-amino- 4'-nitrostilbene disulfonic acid-(222) is used.

Among the mercapto compounds to be used as starting ice materials there are concerned, in the aliphatic series, the saturated, unsaturated, straight chain or branched mercaptans with, for example, 1-10 carbon atoms, which compounds may contain in addition to a mercapto group, further substituents such as halogen atoms or carboxyl or sulfonic acid groups. There may be mentioned allyl mercaptan, amyl mercaptan, thioglycollic acid or thioethylene glycol.

The aromatic hydroxyl and mercapto compounds applicable according to the invention may be derived from any aromatic base compounds, primarily however from benzene and naphthalene. They may contain in addition to an OH- or SH- group, further substituents such as halogen atoms, alkyl groups, etherified hydroxyl groups, acylated or dialkylated amino groups, also carboxylic acid or sulfonic acid groups. There may be specifically mentioned phenol, 0-, m-,v P-chlorophenol, 2:4-dichlorophenol, o-, m-, p-cresol, halogenated cresols, p-bromo-- there are preferably used for the reaction alkylamines,

dialkylamines, hydroxyalkylamines, bis-(hydroxyalkyl)- amines and N:N-dialkyl-alkylene diamines. Both straight chain and also branched, saturated and unsaturated representatives of these compounds with, for example, 1-18 C-atoms can be used. Among them, those with carbon chains of 1-4 C-atoms are especially suitable. There may be mentioned, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylalnine, allylarnine, monoethanolamine, di-isobutylamine and N:N-diethyl-ethylene diamine. Aliphatic amines, such as taurine, for example, which are substituted in the alkyl radical can alsobe used.

The aromatic amines may be monoor polynuclear and if desired may be further substituted. There are used preferably aniline and its nuclear substitution products, as, for'example, oor'p-toluidine, various chloranilines and oor p-anisidine. Naphthylamines, such as aor fi-naphthylamine and their nuclear substitution products can also be. used for the reaction of the invention.

'The heterocyclic amines which can be used according to the invention may contain one or more hetero-atoms. There may be mentioned piperidine, a-pipecoline, morpholine, pyrrolidine, imidazole, benzimidazole, Z-aminothiazole, S-aminotetrazole and tetrahydroquinone. The araliphatic amines are preferably derived from benzylamine, as for example, 4-chloroor 4-methylbenzylamine.

As salts of the products of the invention there are primarily concerned their water-soluble salts with ammonia or amines, but preferably their alkali salts.

For the manufacture of the new compounds according to the invention it is possible, for example, to proceed in such a manner that first as intermediate product a compound is produced of the general formula Patented May 15, 1956.

3 in which v has the significance set forth above. The preparation of this intermediate product can take place, for example, in such av way that one mol of cyanuric chloride isreactedwith 2, mols of 4-amino-4 -nitno- M stilbene disulfonic acidr(2.:2; or a salt; thereof by one of the: conventional methods forthe reaction of cyanur-ic chloride with amines,,for example inthepresence; of Wateror mixtures, of water with organic solvents, such as acetone, and if desired in, the presence of. buffer substances or acid-binding agents, such as sodium. acetate, alkali carbonates or alkali hydroxides and the condensation product. subsequently reacted. in: the prcsence of. buffer substances or acid-binding agents, suchas sodium acetate, alkali carbonates or alkali hydroxides, with onernol of ammonia or one mol of aprimary or secondary amine. It. is also possible first toreact onemolof'cyanurie chloride, with one mol of, an. amino. compound. and, then to condense onemol of. the condensation product thusproduced 2. mols of 4'-amino4 -nitrostilbene: disulfonic ac id(t2;:2 V

For the production of the end product, the nitro groups of the intermediate product I are then reduced to amino groups, which can: be effected, for: example, with iron-- in the presence off an acid; onemol of the reduction product is then condensed with 2 tools of cyanuric chloride and the condensation product obtained in this way reacted with 24 mols of ammonia or 2-4 mols of one of the abovermentioned amino compounds or with- 2 mols. ofanaromatic hydroxyl' compound and: 2. molsof ammonia or 2 mols. of an aminocompound or with 2 molsof an aliphatic or aromatic mercapto compound and 2 mols of ammonia or 2 mols of an amino compound. It is also possible. to react one mol of the reduction product from the intermediate, product I; with 2. mols. of a derivative:

of cyanuric chloride in which 12=, chlorine atoms have been replaced. by reaction with hydroxyl, mercapto ors amino compounds.

By carrying; out the; reaction. sequence set. forth above symmetrical products Willpreferably be produced.

For the manufacture of symmetrical and also asymmetrical compounds, it ispossible toproceed-.such a manner,,for e ampleJhatthe iniermediate product 11: of.

the general formula Nos in whichx and it; have the-significance seti-fortlr above, is first produced.

The production of thisintermediate product cantakeplace in such a manner. that one mol ofgcyanuric: chloride:

is. first. reacted; with l-. mol .ofi- 4'-a.mino-4i-nitrostilbene disulfonic acid-62:2 and then. with. 11-2v mols of. am'-- mom'a or 1 -2. mols of anamino compoundtor. withxl mol: of anaromatic hydroxyl compoundand; I mol of ammonia or 1 mol of an amino compound or with 1 mol of an aliphatic or aromatic mercapto compound and I mol.

of ammonia or 1 mol of an: aminocompound; The.

in which w and x have the significance set forth above, by reacting one mol of the reduction product from the intermediate product II with one mol of cyanuric chloride.

For the synthesis of the end products, the intermediate product III can be condensed with the reduction product from the intermediate product 11 and then reacted further with 1 mol of ammonia or 1 mol of an amino compound. If the substituents w and x in the intermediate product and in the reduction. product are the same, symmetrical compounds are obtained, if they are difierent asymmetrical products are produced.

The end products of the synthesis are also obtainable when 2 molsof the reduction product of the intermediate product II are reacted with 1 mol of cyanuric chloride and subsequently with 1 mol of ammonia or 1 mol of an amino compound.

Finally the. compounds of the first general formula set forth above can also be obtained when: 1 mol. of the intesmediate product III is condensed with 1 mol of 4-amino- 4-nitrostilbene disulfonic acid-(212'), the nitro group reduced in thecondensation productand, in any sequence, 1 mol of cyanuric chloride reacted with- 1 mol of the reduction product and 2-3 mols of ammonia or 2-3 mols of an amino compound or with 1 mol of an aromatic hydroxyl compound and 2 mols of ammonia or 2 mols of an amino compound or with 1 mol of an aliphatic or aromatic mercapto compound and 2 mols of ammonia on 2.mols of an aminocompound.

Mixtures of. compounds in accordance with the invention, which however possess essentially the same properties as the individual compounds, are obtained wheninstead of. individual hydroxyl, mercapto or amino compounds, mixtures. of such compounds are used.

If there isused for the synthesis, instead of the 4- amino-4-nitrostilbene disulfonic acid-(2:2') a 4-aminostilbene disulfonic acid-(222) having an acylamino group in 4 -position, then, in the reaction sequences set forth above, instead of the reduction of the nitro group a hydrolysis of the acylamino-grouptothe free amino-groupmustv be carried out.

The application. of the new products obtainable according to the invention can take place in such amanner that. the material to be improved is impregnated withsolutions,especially aqueous solutions, of' the compoundsspecified and, after hydroextracting or squeezing out,

dried. Forexample, white goods, especially after awash carried out in the customary manner, can be aftertreated with. the products of the invention. The new products. can also be. used for the after-treatment of printed cellulosic materials.

The,v products obtainable according to the present-process can also be applied in the course of the; manufacturing process: ofv the materials to be improved. They are especially suitable for addition to a paper pulpin. the manufacture ofpaper.

In general, small quantities. of theproducts obtainable accord'ing. to the invention sutfice for the production of an improved effect.

Thecompounds obtainable according to the present process can also, on account of their great.substantivity, be added with especial advantage to washing. agents; as washing agents there are suitable, for example, soaps, salts of sulfonated' washing. agents, as, for'example, of sulfonated benzimidazoles substituted on the 2-carbon atom by. higher alltyl radicals, also salts of monocarboxylic acid esters of 4sulfophthalic acid with higher fatty alcohols and furthermore salts of fatty alcohol sul fonates or condensation products of higher fatty acids with aliphatic hydroxy. or amino sulfonic acids or salts of alkylarylsulfonic acids and finally non-ionic washing agents, such as condensation products of alkylene oxides andhigher molecular aliphatic alcohols or amines. Washing agents produced according to the invention can also contain the customary additional substances for washing agents, such as phosphates, pyrophosphates, silicates, perborate or percarbonates.

The manufacture of the mixtures of the Washing agents and optical bleaching agents takes place in a simple manner by mixing and/or grinding of the components. In this operation it may be of advantage for easier distribution to use one or other ofthe components in the dissolved or melted condition.

In general a small addition to the washing agents of the derivatives of 4:4'-diaminostilbene disulfonic acid- (2:2) of the general formula first set forth above proves to be suificient.

N H|N CH=CH NH-E (']NH CH=CH NH:

N 05H our otrr our The washing agents of this invention are used according to the customary washing processes. In this manner the materials to be cleansed can at the same time be washed and bleached.

As materials which can be improved the following may, for example, be mentioned:

Cellulosic materials such as cellulose, paper and textile materials of cotton, linen and regenerated cellulose, including staple fiber. The material to improved may exist in any form, for example in fiber form or also as a film. Moreover the material can be, for example, undyed, dyed or printed.

The following examples illustrate the invention, the parts being by weight:

Example 1 A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 100 parts of ice and 100 parts of water and to the suspension obtained there is gradually added at 0-5 C. within 80 C. and stirring is carried out for'68 hours at 80-85 C.

The condensation product formed is separated by the introduction of sodium chloride, filtered ofi, washed neutral with sodium chloride solution and then reduced. For this purpose, the product is introduced at'90100 C. within one hour into a mixture of 30 parts of glacial acetic acid, 132 parts of iron filings and 1500 parts of water. As soon as the nitro-compound has disappeared, the reaction mixture is rendered alkaline at 60 C. with sodium carbonate, filtered and the acid formed, of the formula C 1 C CHg H: H, O

precipitated from the filtrate by addition of dilute hydrochloric acid, filtered, washed free from mineral acid with water and dried.

A solution of 39 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 200 parts of ice and 200 parts of Water and to the suspension obtained, at 0-5 C., within 10 minutes, the solution of the above-mentioned condensation product, neutralized with sodium carbonate, is gradually added with stirring. Thereupon there is gradually added to the reaction mixture obtained, within one hour, a solution of 11.2 parts of sodium carbonate in 100 parts of water, the addition being made in such a manner that the mixture always reacts neutral to weakly acid, the temperature not being allowed to rise above 10 C. Then 25.2 parts of aqueous 70 per cent monoethylamine solution are introduced, the temperature raised within one hour to 35 C. and stirring carried out for 4 hours at this temperature. The disodium salt produced of the condensation product of the formula 15-20 minutes, a solution, rendered neutral with sodium carbonate, of 80 parts of 4-nitro-4'-aminostilbene-disul tonic acid-(2:2') in 1000 parts of water, while stirring. Thereupon, within one hour, there is gradually added to the reaction mixture obtained, a solution of parts of sodium carbonate in 50 parts of water, in such a manner that the mixture continually reacts neutral to weakly acid. The temperature is subsequently raised within one hour to 30-35 C. and stirring carried out for 4 hours at this temperature, the hydrochloric acid produced being during the entire procedure neutralized by gradual addition of a solution of 5.5 parts of sodium carbonate in 50 parts of water. A clear, amine-free and practically neutral solution is obtained. There are now further added to the reaction mixture 17.4 parts of mor- Example 2 A solution of 39 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 200 parts of ice and 200 parts of water and to the suspension obpholine, the temperature is raised within one hour to tained, at 0-5 C. and within 10 minutes, there is gradually added with stirring the neutral solution of the condensation product of the formula one hour, a solution of 11.2 parts of sodium carbonate 2 in 100 parts of water, the addition being made in such a manner that the mixture always reacts neutral to Weakly acid, the temperature not being allowed to rise above 10 C. Then 12.2 parts of monoethanolamine are introduced, the temperature raised within one hour to 35 C. and stirring carried out for 4 hours at this temperature. ,Tihe hydrochloric acid produced is neutralized by gradual addition of a solution of 11.2 parts of sodium carbonate in 100 parts of water. Finally there are fur- 8 is separated by addition of sodium chloride, filtered; washed neutral with sodium chloride solution and dried.

AO H 0:11

The new product is obtained as a light yellow, watersoluble powder.

By using instead of the aniline used above, equirnolecular quantities of monoethanolamine, monoethylamine or morpholine, products are obtained with similar properties. The products can be used as brightening agents for cellu- 25 losic materials.

Example 3 33.3 parts of the condensation product obtained accordther added to the reaction mixture 372 parts of anlline ing to Example 1, of the formula and the temperature is raised to 80 C. and stirring carried out for 6-8 hours at 80-85 C.

The condensation product formed of the formula are dissolved in 500 parts of water and treated with 4.8 parts of a 70 per cent aqueous mono'ethylarn'ine solution. The temperature is raised within 1 hour to 80 C. and

stirring is carried out for 6-8 hours at 80 85 C. The

condensation product formed of the formula 3-4'h0urs at this temperature, the hydrochloric acid prois separated by addition of sodium chloride, filtered, washed with sodium chloride solution and dried. The new product is obtained as a light yellow water-soluble powder.

The product is suitable as a brightening agent for cellulosic materials.

By using instead of the monoethylamine solution specified above, an equimolecular quantity of ammonia solution, a product with similar properties is obtained.

H: N N

25 duced being continuously neutralized by gradual dropwise addition of a solution of 5.5 parts of sodium carbonate in 50 parts of water. A clear, amine-free and practically neutrally reacting solution is obtained. 23.2 parts of aniline are further added to the reaction mixture, the tem- 30 perature is raised within 1 hour to 80 C. and stirring is carried out for 6-8 hours at 80-85 C.

The condensation product formed, of the formula is separated by addition of sodium chloride, filtered, Washed neutral with sodium chloride solution and dried.

Example 4 A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 100 parts of ice and 100 parts of water and to the suspension obtained 65 Soluble 3 4 there is added dropwise with stirring at -5 C., within Y Instead of quanmy of amlm? -20 minutes, a solution, rendered neutral with sodium timed, an equimolecular q y of mofloethylamme of carbonate, of 120 parts of 4-amino-4'-[2-(fi-hydroxyethylh m m ;p t t similar P pe are -4 i1i -1;3;5. 1 5- i tflben 1.. obtained. The products can be used as brightening agents fonie acid-(2:2) in 1000 parts of water. Thereupon '10 r cellulosic q a there is added dropwise to the reaction mixture obtained,; Products With 51111113! Q P hkewlse Obtamed within 1 hour, a solution of 5.5 parts of sodium car-- when instead of th v ls mentioned '4 bonate in parts of water, the addition being made in (fly Y such a manner that the mixture always reacts neutral to n fi disulfonic 2) a qui lecular quano weakly acid. Subsequently the temperature is raised with-. tity of 4-amino-4'-ig bis-fl-hydroxyethylamino)A-anilinoin 1 hour to 30-35 and stirring is carried out for i The new product is obtained as a light yellow, water 1': 3 S-triazyl-Q6.),-amino-l -sti1bene disulfonic acid- (2;: 2),

4-amino-4'-[.2-monoethylamino-4-anilino: 1: 3 tria-zyl (6)-amino]-stilbene disulfonic acid- (2:2'), or 4-arnino-4- 1 The condensation. product: formed, of the formula [2-(fl-hydroxyethylamino)-4-monoethylamino-1.:3 5 triazyl-(6)-amino]-stilbene disulfonic acid-(2:2') is used and after the condensationthe final chlorine atom on the middle cyanuric rin'g reacted with aniline, monoethyl- V amine, monoethanolamine or ammonia solution.

Example 5 A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 100 parts of ice and 100 parts of water and to the suspension obtained, at 05 C. Within 10-20 minutes, a solution, rendered neutral with sodium carbonate, of 114 parts of 4-amino- 4 [2:4 di-(fi-hydroxyethylamino)-1:3:5-triazyl-(6) aminol-stilbene disulfonic acid-(2:2) in 1000 parts of water added dropwise with stirring; I 'l' liereupon,.to::the= reaction mixture obtained; withirnl h'our, a=solntion-;.of: 5.5 parts ofisodiumcarhlonatein- SD partJs ofawater isadded dropwise in such a manner that the mixture continuously. reacts neutral to weakly. acid.- Subsequently the temperature israisedwithin 11 hour. to. -35 Grand-stirring. is carried. out for 3-4 hours at this temperature,. the hydrochloric acid produced. being, during. this. time, continuously neutralized by the gradual dropwise addition of a solution of 5.5 parts of sodiumcarbonate in. 50" parts of water. A clear, amine-free and' practically neutra'lly reacting solutionis obtained. 15.2 parts of monoethanolamine are'now added'to the reaction mixture;.tlie*tempe'rature is raised within I hour to 80 C1 and stirring is carried on for 6 7 hours at 80 -90" 0'.

1 water.

to 304 5 and stirring: carriediont fon 3-4 hoursat: this temperature, the hydrochloric: acid produced being. continuously neutralized during:this time: by the? gradual:

. dropwis'e addition of a; solution: of: 5 parts of: sodium:-

A. clean; amine-free and? is separated by addition of sodium chloride, filtered, washed neutral with sodium chloride solution and dried. The new product is obtained as a light yellow, Watersoluble powder.

By using instead of the final quantity of monoethanolamine equimolecular quantities of aniline or monoethylamine, products are obtained with similar properties. The products can be used as brightening agents for cellulosic materials.

Example 6 A solution of 18.5 parts of cyanuric chloride in parts of acetone is stirred intoa mixture of 100 parts of ice and 100 parts of water and to the suspension obtained, at 05 C. within 10 minutes, a solution, rendered neutral with sodium carbonate, of 60 parts of 4-amino-4'-[2- (fl-hydroxyethylamino) 4 anilino-1:3:5-triazyl-(6)- aminoJ-stilbene disulfonic acid-(2:2') in 500 parts of water is added dropwise with stirring. Thereupon there is added dropwise to the reaction mixture obtained, within 1 hour, a solution of 5.5 parts of sodium carbonate in 50 parts of water, the addition being made in such a manner that the mihture reacts continually neutral to weakly acidi To the suspension-wliich new" no longer" contains any free amino groups, there is added dropwi'se" withstirring at" 10 16 6. within l-ll minutes; a sol'utio'n; rendered" neutral with" sodium carbonate; 0t 5356 parts carbonate in So -rants at: water.

13 practically neutrally reacting solution is obtained. 23.3 parts of aniline are'further added to the-reaction mixture, the temperature is raised within 1 hour to 80 C. and stirring is carried on for 6-8 hours at80-85 C.

The condensation product formed of the formula 14 with sodium carbonate, of 58.3 parts of 4-amino-4"-[2 ethylamino 4 anilino 1:3:5 triazyl (6) amino] stilbene disulfonic acid (222) in 500 parts of water added dropwise with stirring. Thereupon there is added to the reaction mixture obtained, within 1 hour, a soluis separated by addition of sodium chloride, filtered, washed neutral with sodium chloride solution and dried. The new product is obtained as a water-soluble light yellow powder.

By using instead of thefinal quantity of aniline an equimolecular quantity of monoethylamine, a product is obtained with similar properties. The products can be used as brightening agents for cellulosic materials.

Products with similar properties are obtained when 1 mol of cyanuric chloride is condensed with 1 mol of 4- amino 4 [2 ethylamino-4-anilino-l:3:5-triazyl-(6)- aminoJ-stilbene disulfonic acid-(2:2) and 1 mol of 4- amino 4 [2:4-di-(B-hydroxyethylamino)-1:3 :S-triazyl- (6)-aminol-stilbene disulfonic acid-(22) and then reacting the final chlorine atom on the middle cyanuric ring with aniline or monoethanolamine.

Example 7 A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone is stirred into a mixture of 100 parts of ice and 100 parts of water and to the suspension obtained, at -5 C. within 10 minutes, a solution, rendered neutral tion of 5.5 parts of sodium carbonate in 50 parts of water, the addition being made in such a manner that the mixture continuously reacts neutral to weakly acid. Into the suspension which now no longer contains any free amino groups, there is introduced dropwise at 10-15 C. within 10 minutes a solution, rendered neutral with sodium carbonate, of 61.3 parts of 4 amino 4 [2 bis ()3 hy droxyethylamino) 4 (B hydroxyethylamino) 123:5 triazyl (6) amino] stilbene disulfonic acid (212) in 500 parts of water, with stirring. The temperature is then raised within 1 hour to 30-35 C. and stirring is carried on for 3-4 hours at this temperature, the hydrochloric acid produced being, during the whole of this time, continuously neutralized by gradual dropwise addition of a solution of 5.5 parts of sodium carbonate in 50 parts of water. A clear, amine-free and practically neutrally reacting solution is obtained. 21.8 parts of morpholine are now further added to the reaction mixture, the temperature raised within 1 hour to C. and stirring carried on for 6-8 hours at 80-85 C. The condensation product formed of the formula 16 isseparated by addition of sodium chloride, filtered, monoethanolamine are now added to the reaction mixture, washed neutral with sodium chloride solution and dried. the temperaturevr aised within ,1-2 hours to 60 C. and The new product is obtained as a light yellow waterstirring carried on for 15-18 hoursat 60-6 5 C., V soluble powder. The condensation product formed of the -formula j on, I V I 7' r a t Q Q t r N N N OINB lN t t IITH NH N801 CH: IE!

I H CH: J) H I OH:

NaOgS -t t- N 5 By using instead of the above mentioned quantity of is separated by addition of sodium chloride, filtered,

morpholine an equimolecular quantity of diethylamine, washed neutral with sodium chloride solution and dried. a product is obtained with similar properties. The prod The new product is obtained .as a light yellow wateructs can be used as brightening agents for cellulosic matel bl powden v r Hals- By using instead'of the p-cresol equimolecular quanti- Example 8 40 ties of phenol, thio-p-cresol or thioethylene glycol, prod- Following the directions of Example 1, th ond n anets with similar properties are obtained. The products tion product of the formula can be used as brightening agents for cellulosic materials.

. N\ s i V H:NO-CH=CH -NHC|) -NHQOihOHQNHa V N N :15: 80:11 \O/ 80:11 01H r 7 1 v is produced by reacting together 2 mols of 4-nitro-4- Example 9 amino-stilbene disulfonic acid-(2:2), 1 mol of cyanuric chloride and 1 mol of monoethylamine and the condensation product obtained is reduced by the process of Bchamps.

43 parts of the condensation product thus obtained are converted into aneutrally reacting solution in 250 parts of water with sodium carbonate and this solution is added dropwise, within l020 minutes at 0-5 C., to a suspension which has been produced by stirring 18.5 parts of cyanuric chloride dissolved in 100 parts of acetone into a mixture of 100 parts of ice and 100 parts of water. Thereupon, to the reaction mixture obtained, within 1 65 hour, a solution of 5.5'parts of sodium carbonate in 50 parts of water is added dropwise in such a manner that the mixture continuously reacts neutral to weakly acid.

A solution of 18.5 parts of cyanuric chloride in 100 ice and 100 parts .of water and to the suspension obtained,

- att 0,5 C. within 10 minutes, a solution rendered neutral with sodium carbonate, of 59.8 parts of 4 amino 4 [2 phenoxy 4 3 hydroxyethylamino) 123:5 tri azyl (6) amino] stilbene disulfonic acid (2:2') in 500 parts of water is added dropwise with stirring. Thereupon there is added dropwise to the reaction mixture obtained, within 1 hour, a solution of 5.5 parts of sodium carbonate in 50 partsof water, the addition being added in such a manner that the mixture continuously reacts neutral to weakly acid. To the suspension which now no longer contains any free amino groups, there is added dropwise with stirring at l0-15 C. within 10 minutes, a

Tofhe ,Suspension'which now no longer contains any free solution, rendered neutral with sodium carbonate, of 53.6 amino groups, 10.8 parts of p-cresol are added. Then the parts of 4 amino diethylamino :3: tri temperature 1s raised within 1 hour to 40 C. and stirring azyl (6) amino] tjlb di lf i id 2;2') i is d O for 4 hours at the hydwchlol'ic 500 parts of water. Then the temperature is raised within acid produced being continuously neutralized during the 1 h t 3() 35 C, and stirring i carried on for 34 whole time by the gradual dropwise addition of 100 parts hours at this temperature, the hydrochloric acid produced of N-sodium hydroxide solution. A further 15.2 parts of being continuously neutralized during the whole of this parts of acetoneis stirred into a mixture of parts of' h the r dual dran dd t on f a u i n a wa saa ti a 9 e 91 o a i l d w th 1 9! of P of $941 9; c rbaa e 59 Pa i a r A 9 w Q-. i n? d s o aid:(2=2 t 0-19 amine-free and practically neutrally reacting solution is Q WEI? l f Ph at i0: Dd, 1 3 91 9 obtained. 15.2 parts of monoethanolamine are now fur- .m n stl analamw -55 a b q i i 9 p? ther added to the reaction mixture, the temperature is 5 u b -F ih Q B raised within 17-2 hours to 60 and stirring is carried E Q Pl on for l5.18 hours at 60-65 C. The condensation product of the formula N N\ NHC/ C NH 011 01; NH- -C 0 I ll I If N N N 0;};2 0;1 Ia C (i) H, H, H2 l H v H The condensation product formed, of the formula is produced when, following the directions of Example 6,

CH: i C-NH N 1 NH H: (BB;

is separated by addition Qf sodium chloride, filtered, 1 mol of cyanuric chloride is condensed with 1 mol of washed neutral with sodium chloride solution and dried. 4 amino 4 [2 (p3 hydroxyethylamino) 4 anilino The new product is obtained as a light yellow water- 1:3:5 triazyl (6) amino] stilbene disulfonic acid soluble powder. (2:2'), 1 mol of 4-nitro-4'-amino-sti1bene disulfonic acid- By using instead of the above ,mentioned quantity of 60 (2:2') and 1 mol of monoethanolamine with reduction monoethanolamine equimolecular quantities of monoof the condensation product obtained by the method of ethylamine or ammonia solution, ,products are obtained Bchamps. with similar properties. The products can be used as A solution of 18.5 parts of cyanuric chloride in 100 bn'ghtening agents for cellulosic materials. parts of acetone is stirred into a mixture of 100 parts of ,B QQQS I with 1 9PEi$ ar likewise abtaia i9? s 9. P t -9 ate n 1 9 $1 aa pa s a ab a nsr when instead of the 4 amino 4' [2:4 iiethy lamir1o tat. 0r5 l O Z-O minutes .there 1:32-5 triazyl (6) amino] stilbene disulfonic [acid With stirring a solution, rendered neutralwith s'baiumqar- (2:2') equimolecular [quantities are used of .4-amino-4'- bonate, of 119.3 parts of the condensationipro eve [2 phenoxy 4 (.fi,..-hydroxyethy lamino) 1: 3 :5 tn' roduced in 1000 parts of water. Then to reaction azyl (6) amino] stilbenedisulfonicacid (2:2') or mixture obtained, within 1 hour, a solution of 5.5 pairs 4 amino 4' [2 phenyl --thi o.- 4 ethylamindl:3: 5 of sodium carbonate in 50 parts of water is added drops -en d w i a i d 2 :Wi su h ams t ha i tu s Ql1m Q9 Y The initially mentioned 4 amino: 4 2,,--p l 1enoxy eutral-towealgly acid. Tothe suspensipn ligvhich'now o 4 ()3 hydroxyethylamino) 1:3:5 ,fl'iazyl; ,(6) longer contains any free amino groups, 12. par s q.

amino] stilbene disulfonic acid (252') is produced by methylthioph enol are added, Then'the tem erature is raised within 1 hour to 40 C. and stirring is carried on for 4 hours at 40-45 C., the hydrochloric acid produced being neutralized throughout the whole time by the :gradual dropwise addition of 100 parts of N-sodium hydroxide solution. 152 parts of monoethanolamine are now further added to the reaction mixture, the temperature is raised within 1-2 hours to 60 C. and stirring is carried on for 15-18 hours at 60-65 C.

The condensation product formed, of the formula is separated by addition of sodium chloride, filtered,

washed neutral with sodium chloride solution and dried. 3

The new product is obtained as a yellow water-soluble powder.

A product with similar properties is likewise obtained,-

of the formula iii.

when instead of 4-methylthiophenol an equivalent quantity of monoethanolamine is used and the final chlorine atom is not replaced.

The products can be used for the brightening of cellulosic materials.

Example 11 Undyed cotton yarn is treated at room temperature for about 4 hour, in a bath ratio of 1:30, in a bath which contains per litre 0.01 gram of the condensation product NH-C 20 obtained according to Example 6. After rinsing and drying, the yarn thus treated possesses a higher white content than the corresponding untreated material.

Example 12 The sodium salt of Z-heptadecyl-N-benzylbenzimidazyldisulfonic acid is mixed with 0.05-0.5 per cent. of the condensation product obtained according to Example 5. Undyed textile material which has ben washed in the NH-CHa-C Ha-OH customary manner with the mixture obtained, exhibits a brighter appearance than textile material which has been washedwith the. above specified sodium salt alone.

Example 13 Cotton is washed at the boil, in a bath ratio of 1:40, in

NBOaE 33.3 per cent. of soap, 11.0 per cent. of calcined sodium carbonate,

70 14.0 per cent. of sodium pyrophosphate,

7.0 per cent. of sodium perborate,

3.0 per cent. of magnesium silicate, I 1.0 per cent. of the product obtainable according to Example 4 or 6, and

75 31.6 per cent. of water.

2,745,830 21 2.2 The material'is rinsed and dried. ther, each of x and y is a member selected from the group The cotton thus treated possesses a whiter appearance consisting of Cl, NHz, lower alkylamino, lower (hythan similar material which has been washed with the droxyalkyD-amino, morpholino, mononuclear carbosame washing agent but not containing the addition of cyclic aromatic amino, mononuclear carbocyclic arylggry the product of Example 4 or 6. 5 attached to the ariazine ring by the aryloxy oxygen atom, and mononuclear carbocyclic arylmercapto attached to Example 14 the triazine ring by the mercapto sulfur atom, the respec- A paper pulp, containing 100 parts of paper, in a tive ami groups being attached to the ia ae. ring by hollander, is first subjected to the addition of 2 parts of the amino nitrogen atom; and wherein each'of v, $9,217, y resin glue and after 15 minutes 2-4 parts of the product and z is free from groups which impart dyestuli char obtainable according to Example 3, dissolved in about 80 acteristics to the molecule. parts of water, are added. After a further minutes 3 2. An alkali metal salt of a compound of the formula parts of aluminum sulfate are added. The paper pulp thus wherein each of at least two Us represents a radical of treated then passes to the paper machine by way of the the formula heater.

Paper subjected to this treatment has a higher white content than untreated paper.

By using instead of the product'produced according to 41) Example 3, a compound obtainable according to Example 4, 5 or 6, a similar effect is obtained. and each of the remaining Us represents NH-phenyl,

What is claimed is: m being a whole number of at the most 2. 1. An alkali metal salt of a derivative of 4:4-diamino- 3. An alkali metal salt of a compound of the formula U4? -NHQCEOH33NH- \(IJ-N'HQCH=CHONH% (ll-U N N N N N N 01H 03H 01H A0115! 5 t F U U U gg gg z mud-(2:2) whlch corresponds to the wherein each of at least two US represents a radical of :r|O \C|!-NH- ?CH=CH-QNH-("3/ (|3-NHQCH=CH: NH-(l) CII-g k 0,3 sou! 01H 0,11 k c c c I I I l0 i7 2 wherein each of v, w and 1 represents an amino radical the formula attached by the amino nitrogen atom to the adjacent triazine ring and having at least one hydrogen atom attached to said amino nitrogen atom, said amino radical being selfcted from the group consisting of alkyl' :50 and each of the remaining U s represents NH-ethyl, m ammo, lower y yynmorpholmo. and being a whole number of atthe most 2.

mononuclear carbocyclic aromatic amino; wherein, fur- 4. The compound of the formula I K I HNO CNHOOH=CH NH-C C--NH 1. 4d .1 Q i. i.

C/ V N :N OaN I -IH 1 m Na0;S SJH: (kHz H NBOQS N can: NHC CI -IH l 1'-': c in 6H] (3H,

2,745,830 23 24 5. The compound of the formula 25 26 7. The compound of the formula N N 13111-0 \CNHQ-CH=CHONHC% 0 NH kg N g b2 1% S0aNa o c 0 1 1]; 11111 NaO S zHn H! H: EH AH H N80; in H: N 5H: NEE-0% \J-JTH il in EH3 $11, $11

8. Thecompound of the formula N N C \C-NH OH-CH NH-G 0 NH 1!: 1 1 1% \Q/ 03KB 0N8 .{T\ $11 N30 Gig 0:: H

9 an an EH NaO N 183- d C- H 1!: C62 GH,

H B3 AH 611 References Cited in the file of this patent UNITED STATES PATENTS 2,376,743 Wendt May 22, 1945 

1. AN ALKALI METAL SALT OF A DERIVATIVE OF 4:4''DIAMINOSTILBENE-DISULFONIC ACID-(2:2) WHICH CORRESPONDS TO THE FORMULA 